Astruc D. - Modern arene chemistry (2002)(en)

The History of Benzene

1

The History of Aromaticity

5

1.2

Truxene and Truxone: Venerable Prototypes 21

1.3

Other Examples 23

1.4.1

Experimental Observations and a Working Hypothesis 27

1.4.2

Guidance from Calculations 29

2.2

Cyclopentadienyl Cations 33

2.3

Fulvene and Spiroannelated Cyclopentadiene Derivatives 37

vi

Contents

Polyunsaturated Di-, Tri-, and Oligoquinanes 38

2.4

2.4.1

Pentalene, Pentalenediide, and Pentalene Metal Complexes 39

2.4.2

Acepentalene, Acepentalenediide, and Acepentalene Metal Complexes 42

2.4.3

Generation of C20-Fullerene 44

References

50

3

The Suzuki Reaction with Arylboron Compounds in Arene Chemistry 53

Akira Suzuki

Abstract

53

3.2

Reactions with Aryl Halides and Triflates: Synthesis of Biaryls 54

3.2.1

Aromatic–Aromatic Coupling 54

3.2.2

Aromatic–Heteroaromatic and Heteroaromatic–Heteroaromatic Couplings 65

Withdrawing Substituents 76

3.2.4

Modified Catalysts and Ligands 80

3.2.5

Solid-Phase Synthesis (Combinatorial Methodology) 84

3.3

Reactions with 1-Alkenyl Halides and Triflates 88

3.4

Reactions with Aryl Chlorides and Other Organic Electrophiles 93

3.6

Applications in Polymer Chemistry 99

References

102

4

Palladium-Catalyzed Amination of Aryl Halides and Sulfonates 107

John F. Hartwig

Abstract

107

4.1.1

Synthetic Considerations 107

Halides 108

4.1.3

Novel Organometallic Chemistry 109

4.1.4

Organization of the Review 109

4.2.1

Early Palladium-Catalyzed Amination

110

4.2.2

Initial Synthetic Problems to be Solved

111

4.3.1

Early Work 111

4.3.1.1

Initial Intermolecular Tin-Free Aminations of Aryl Halides 111

4.3.1.2

Initial Intramolecular Amination of Aryl Halides

112

4.3.2

Second Generation Catalysts: Aryl Bis-phosphines

112

4.3.2.1

Amination of Aryl Halides

112

4.3.2.2

Amination of Aryl Triflates

115

4.3.2.3

Amination of Heteroaromatic Halides 116

4.3.2.4

Aminations of Solid-Supported Aryl Halides 119

4.3.2.5

Amination of Polyhalogenated Aromatic Substrates

119

4.3.3

Third-Generation Catalysts with Alkylmonophosphines 119

4.3.3.1

High-Temperature Aminations Involving P(tBu)3 as Ligand

120

4.3.3.2

Use of Sterically Hindered Bis(phosphine) Ligands

120

4.3.3.3

P,N Ligands and Dialkylphosphinobiaryl Ligands

121

4.3.3.4

Phenyl Backbone-Derived P,O Ligands 123

4.3.3.5

Low-Temperature Reactions Employing P(tBu)3 as a Ligand

124

4.3.3.6

Heterocyclic Carbenes as Ligands 124

4.3.3.7

Phosphine Oxide Ligands

128

4.3.4

Heterogeneous Catalysts

129

4.4.1

Amides, Sulfonamides, and Carbamates

130

4.4.2

Allylamine as an Ammonia Surrogate

131

4.4.4

Protected Hydrazines 132

4.5

Amination of Base-Sensitive Aryl Halides

135

4.6

Applications of the Amination Chemistry

136

4.6.1

Synthesis of Biologically Active Molecules

136

4.6.1.1

Arylation of Secondary Alkylamines

136

4.6.1.2

Arylation of Primary Alkylamines

138

4.6.2

Applications in Materials Science

141

4.6.2.1

Polymer Synthesis 141

4.6.2.2

Synthesis of Discrete Oligomers 143

4.6.2.3

Synthesis of Azacyclophanes 146

4.6.2.4

Synthesis of Small Molecules for Materials Applications 146

4.6.3

Palladium-Catalyzed Amination in Ligand Synthesis

147

4.7

Mechanism of Aryl Halide Amination and Etheration

149

DPPF) and its Mechanism 149

4.7.2

Formation of Amido Intermediates 151

4.7.2.1

Mechanism of Palladium Amide Formation from Amines 151

4.7.3

Reductive Eliminations of Amines from Pd(II) Amido Complexes 152

4.7.4

Competing b-Hydrogen Elimination from Amido Complexes

155

4.7.5

Selectivity: Reductive Elimination vs. b-Hydrogen Elimination

156

4.7.6

Overall Catalytic Cycle with Specific Intermediates 158

viii

Contents

From Acetylenes to Aromatics: Novel Routes – Novel Products 169

5

Henning Hopf

Abstract 169

5.4

Bridged Aromatic Hydrocarbons Containing Triple Bonds (Cyclophynes) 187

References 192

6.2

Arylated Tetraethynylethenes

198

6.2.1

Nonlinear Optical Properties

198

6.2.2

Photochemically Controlled cis–trans Isomerization: Molecular Switches 199

6.2.3

Electrochemically Controlled cis–trans Isomerization

201

6.3

Tetraethynylethene Dimers

202

6.4

Two-Dimensional Sca olding: Expanded Carbon Cores

204

6.4.1

Perethynylated Dehydroannulenes

204

6.4.2

Perethynylated Expanded Radialenes

205

6.4.3

Cyclic Platinum s-Acetylide Complex of Tetraethynylethene

208

6.5

Linearly p-Conjugated Oligomers and Polymers: Poly(triacetylene)s 209

6.5.1

Lateral Aryl Substitution

210

6.5.2

Aromatic Spacer Units

210

6.5.3

Donor–Donor and Acceptor–Acceptor End-Functionalization

212

7.1.1

Scope and Coverage of this Review 217

7.1.2

Historical Perspective 217

Carbyne Complex 220

7.2.2

Synthesis of Diarylalkynes Utilizing the Mori System 221

7.2.4

Alkyne-Bridged Polymers by ADIMET

225

7.3

Reactivities of PPEs 229

7.4

Solid-State Structures and Liquid-Crystalline Properties of the PPEs 231

7.4.1

Organometallic Poly(aryleneethynylene)s

231

7.5

Spectroscopic Properties of Dialkyl-PPEs 235

7.5.1

UV/vis Spectroscopy of Dialkyl-PPEs 237

7.5.2

Fluorescence Spectroscopy: The Excited State Story 240

and Nanowires 242

7.7

PPE-Based Organic Light-Emitting Diodes (OLEDs) 244

7.8

Conclusions and Outlook 245

References 247

8.2

Mechanism and Chemoselectivity of the Benzannulation 253

8.3

Scope and Limitations

257

8.3.1

The Carbene Complex

257

8.3.1.2

The Carbene Ligand 259

8.3.1.3

The Chromium Template 263

8.3.2

The Alkyne 264

8.3.5

Thermal and Photochemical Benzannulation 271

8.3.6

Subsequent Transformations

271

8.4

Typical Experimental Procedure 272

8.5

Synthesis of Specific Arenes

273

8.5.3

Annulenes and Dendritic Molecules 278

8.5.4

Angular, Linear, and Other Fused Polycyclic Arenes 279

8.5.5

Fused Heterocycles 283

8.6

Synthesis of Biologically Active Compounds 285

8.7

Summary and Outlook 291

References

292

9

Osmiumand Rhenium-Mediated Dearomatization Reactions with Arenes 297

Mark T. Valahovic, Joseph M. Keane, and W. Dean Harman

Abstract

297

9.2

{Os(NH3Þ5}2þ – The Pentaammineosmium(II) Fragment 298

9.2.1

Preparation of h2-Arene Complexes 298

9.2.2

Binding Selectivity 298

9.2.4

Benzene and Alkylated Benzenes 300

9.2.7.1

Electrophilic substitution 315

9.2.7.2

4H-Anilinium Michael Additions

316

9.2.7.3

Electrophilic Addition Reactions

318

9.2.7.4

Michael–Michael–Michael Ring-Closure 318

9.2.8.1

Electrophilic Substitution Reactions 318

9.2.8.2

Michael Addition Reactions 320

9.2.8.3

o-Quinone Methide Complexes 323

9.3.2

Preparation of h2-Arene Complexes 324

9.3.3

Quadrant Analysis 324

9.4

Concluding Remarks

328

References

328

10

The Directed ortho Metalation Reaction – A Point of Departure for New Synthetic

Aromatic Chemistry

330

Christian G. Hartung and Victor Snieckus

Abstract

330